Polymer composition

ABSTRACT

Polymer composition comprising a) 10-99.99% by weight of at least one polyolefin, b) 0-50% by weight of a thermoplastic that is not a polyolefin, c) 0.005-1% by weight of per se known polymer additives, as well as an additional component chosen among d) at least one polybranched organic/inorganic hybrid polymer which has an inorganic core carrying organic branches, the core and branches forming a particulate structure, or/and e) a fat-soluble metal compound prepared by reacting a metal salt and an acidic, organic compound in a process in which a suitable oxidation agent ensures that all the metal in the end product is present in its highest stable oxidation state at standard conditions (25° C. and maximum 98% humidity).

RELATED APPLICATION

This application claims priority to PCT application PCT/NO2005/000127,filed Apr. 18, 2005, which claimed priority to Norwegian patentapplication 20041556, filed Apr. 16, 2005.

The present invention concerns a polymer composition comprising at leastone polyolefin and at least one component that is not a polyolefin.

According to second aspect the invention concerns adaptation ofdifferent properties of a polymer composition by suitable choice of theabove mentioned components. According to a third aspect the inventionconcerns use of such polymer compositions.

BACKGROUND

Polymer materials are utilized in an increasing number of categories ofproducts, such as components for cars, boats, airplanes, within theelectronics industry and other advanced industry as well as in paintsand other coatings, for special packaging etc. The uses of polymermaterials in new categories of products are only limited by the productproperties. It is thus a continuous need for development of polymerproducts with improved properties e.g. with respect to increased scratchresistance, improved weather resistance, increased UV resistance,increased chemical resistance and improved properties with respect toanti oxidation, anticorrosion etc.

In addition to pure polymer materials there has also been developedproducts based on materials that may be described as hybrids betweeninorganic and organic materials, which means that these materials aremacro molecules that may have an inorganic core and organic branches.

Organic polymer molecules with branched structures have an enormouseconomical growth potential, particularly as components in newmaterials. So-called dendrimers are important examples of such polymermolecules with a perfectly branched structure as well as hyperbranchedpolymers with statistically progressive branching. Both dendrimers andhyperbranched polymers are denoted dendritic polymers. Dendritic (fromGreec: “dendron”=tree) characterizes the principle of a progressivebranching that is more or less perfect (G. R. Newkome, C. N. Moorefield,F. Vögtle, “Dendrimers and Dendrons: Concepts, Syntheses, Applications”,Wiley-VCH, Weinheim, (2001)). Formula 1 illustrates the principledifference between linear polymers and dendritic polymers (hyperbranchedpolymers and dendrimers).

FORMULA 1

linear polymers

Hyperbranched polymers

dendrimers K germ (the beginning of the polymer molecule) L linearpropagation D dendritic branching T termination (the end of the polymermolecule)

Dendritic polymers are particularly interesting because the T units maycarry functional groups and the density of available functional groupsper weight or volume unit of the polymer is much higher than what is thecase for linear polymers. Functional T groups may be used to impart afunction in a material, like an antioxidant, a UV absorber, or a radicalscavenger as described in WO publication No. 02092668.

Alternatively the T groups may be used as very efficient cross-linkersof organic materials like epoxy resins or polyurethanes or ascross-linkers for thermoplastics. Due to the high degree ofcross-linking between dendritic polymers and such organic compounds thedendritic polymers are superior cross-linkers compared to conventionalcross-linkers like polyamines, polyalcohols, or multifunctionalacrylates. Higher degree of cross-linking of an organic material like across-linked thermoplastic improves properties such as chemicalresistance, weather resistance and wears resistance and makes thematerial useful for applications at higher temperature. (Hans Zweifel(ed.), Plastics Additives Handbook, Carl Hanser Verlag, München, (2001),725-811). The T groups may also be used to organize the dendriticpolymers in a network. As component in a material the dendritic polymerthus may induce improved barrier properties. Alternatively suchdendritic polymers may be used as a binder or as a component in athermoset plastic.

Dendrimers are usually manufactured in relatively complicated andexpensive synthesis comprising several steps. The process conditionsmust be maintained very accurately in order to achieve a perfectprogressive branch structure. Their industrial applications aretherefore limited.

A general way of manufacture of hyper branched polymers was earlydescribed by Flory (P. J. Flory, Principles of Polymer Chemistry,Cornell University, (1953)). The polymerization of an AB₂ monomer whereA may react with B but where the reactions between A and A and between Band B are precluded, leads to a hyperbranched polymer.

Another way of manufacturing hyperbranched polymers involves theutilization of a reactive monomer that also carries an initiator, aso-called “inimer”. One example is the base catalyzed reaction betweenthe inimer glycidol and the germ trimethylol propane as illustrated byFormula 2.

FORMULA 2

K germ (the beginning of the polymer molecule) L linear propagation Ddendritic branching T termination (the end of the polymer molecule)

Hyperbranched polymers made in this way have properties that are quitesimilar to corresponding dendrimers (A. Sunder, R. Hanselmann, H. Frey,R. Mühlhaupt; Macromolecules, (1998), 32, 4240). This implies a muchlower viscosity than that of linear polymers with a comparable number offree available HO-groups. A characteristic feature in the manufacturingprocess is that the inimer glycidol must be added very slowly to thegerm and in a very thin dilution. Thus, the cost-efficiency of theprocess is severely reduced which is why the utility of hyperbranchedpolymers in industrial applications is quite limited.

It is previously known to perform certain modifications of the T groupsof hyperbranched polymers. J.-P. Majoral, A.-M. Caminade and R. Kraemer,Anales de Química Int. Ed., (1997), 93, 415-421 describe thefunctionalization of dendrimers containing phosphorus. Thefunctionalization of the T groups can be made with identical/similarchemical groups or with different chemical groups.

FR 2761691 discusses dendrimers with functional groups at the surfacethat are modified through a reaction with cyclic thioesters. Thereaction leads to a dendrimer surface with thiol groups that areattached to the dendrimer by amide or amine bondings. The products maybe used as antioxidants. The dendrimers described are of the typepolyamidoamine dendrimers (PAMAM dendrimers). PAMAM dendrimers containtertiary amines that comparatively easy may be degraded after conversionto quaternary ammonium salts or aminoxides (A. W. Hofmann, JustusLiehigs Ann. Chem. (1851), 78, 253-286; A. C. Cope, E. R. Trumbull, Org.React. (1960), 11, 317-493; A. C. Cope, T. T. Foster, p. H. Towle, J.Am. Chem. Soc. (1949), 71, 3929-3935). Quaternary ammonium salts oraminoxides from amine based dendrimers can be formed when additives ofamine based dendrimers are incorporated/compounded into thermoplasticswith subsequent processing of the thermoplastics (e.g. film blowing,extrusion, casting). Such a degradation on one hand leads to a partialdeterioration of the dendrimer core and on the other hand to formationof degradation products which may leak out and thereby reduce thesurface quality of the polymer product. In addition tertiary amines mayduring processing of the thermoplastic form free radicals bydecomposition of hydro peroxides (A. V. Tobolsky, R. B. Mesrobian,Organic Peroxides, (1954), Interscience Publishers, New York, p.104-106). Dendrimers and hyperbranched polymers that contain tertiaryamines thereby may induce an unintended degradation of thermoplasticsduring their processing, storage or use.

WO 01/48057 discusses multifunctional stabilizers against thermaloxidative degradation based on a core structure containing tertiaryamines. As mentioned above this may lead to an unintended degradation ofthe core structure during processing, storage or use of (the)thermoplastics. The molar weight of a typical stabilizer manufactured inaccordance with WO 01/48057 is 1246 g/mole.

WO 97/19987 discusses combinations of polymer additives and modifieddendrimers that may be used in polymer materials. In the exemplificationof WO 97/199987 the dendrimers are based on polypropyleneimine (PPI) of3^(rd), 4^(th) and 5^(th) generation thereby including 16, 32, and 64terminal amine groups. The core structure contains tertiary amines whichmay lead to an unintended degradation of the core structure duringprocessing, storage or use of thermoplastics. The modification of thePPI dendrimer with a fatty acid to form a multifunctional fatty acidamide may bee conducted by means of heating in a suitable solvent. Thetertiary amine groups in the core structure of the dendrimer and primaryamine groups at the dendrimer surface may in presence of oxygencontribute to partial degradation of the dendrimer structure. Asexplained above free radicals may be formed by decomposition of hydroperoxides. Such a partial degradation is indicated by a faint brown oryellow colour of the modified PPI dendrimer, like in examples I, XI, andXII in WO 97/19987. Typical molecule weights for modified PPI dendrimersin WO 97/19987 are in the range 10 000 to 40 000 g/mole. In WO 02/092668surface activated hyperbranched or dendritic stabilizers comprising atleast one additive group and a hyperbranched or dendritic core isdiscussed. In the exemplification of WO 02/092668 only dendritic coresbased on 2,2-bis-(hydroxymethyl)-propionic acid is used. The dendriticcore and the bonding to the additive group thereby are mainly based onester bondings, which make the stabilizer sensitive to hydrolysis. Inaddition the exemplification of WO 02/092668 shows that the molecules ofthe prepared stabilizers as determined by gel permeation chromatographyis between 1000 and 1500 grams/mole.

One type of particulate polymers with properties corresponding to theproperties of hyperbranched polymers comprises an inorganicSi_(x)O_((1.5)x)-core with one T group per Si atom and is known as POSS(polyhedral oligosilesquioxanes). The most common compound of this classis a POSS with x=8 and substantially cubic structure (C. Sanchez, G. J.de A. A. Soler-Illia, F. Ribot, T. Lalot, C. R. Mayer, V. Cabuil; Chem.Mater., (2001), 13, 3066). The manufacture of POSS is expensive (M. C.Gravel, C. Zhang, M. Dinderman, R. M. Laine; Appl. Organometal. Chem.,(1999), 13, 329-336 and WO 01/10871) and their industrial applicabilityis therefore limited.

Another type of particulate polymers with properties corresponding tothe properties of hyperbranched polymers consists of an inorganicSi_(x)O_((1.5)x) core that carries one T group per Si atom and may bemanufactured in a sol-gel process through controlled hydrolysis andcondensation of a silane with a structure:X—B—Si(—Y)₃

Where Y is chosen among hydrolysable residues and X—B basicallycorresponds to the T group. The process is described e.g. in Applicant'sown WO publication No. 0208343. Sol-gel processes may be cost efficientso that they may be conducted in industrial scale from favourable rawmaterials and under mild conditions, i.e. without use of high pressuresor high temperatures and without particular precautions like extremedilution or the like. Thus particulate polymers with propertiescorresponding to properties of hyperbranched polymers manufactured bysol gel processes are industrially applicable in many areas.

Many examples of utilization of sol gel products in polymer products areknown (DE 199 33 098, EP 666 290). Normally the main focus is placedupon the inorganic Si_(x)O_((1.5)x) core with a size in the nanometerrange and thereby upon the sol-gel product as inorganic nano particle,cf. DE 199 33 098 and EP 486 469. The inorganic residues X—B aretypically used to anchor the sol gel products in an organic matrix, cf.EP 486 469.

The sol gel process involving hydrolysis and condensation of a silane inwhich the X—B group contains one or more amide groups is particularlysimple because no external catalyst is needed and because the processmay be conducted at ambient temperature or under moderate heating. Oneexample is controlled hydrolysis and condensation of γ-aminopropyltrialkoxysilane as described in applicant's own patent application, WOpublication No. 0208343. Controlled hydrolysis and condensation ofsilanes in which the X—B groups contains one or more amide groupstypically leads to a sol in which the resulting particulate polymerproduct has an organic/inorganic structure (hybrid polymer) that iscomparable with a hyperbranched polymer product with a number of more orless free amine groups in the T groups. Such organic/inorganic hybridpolymers exhibits a large number of functional T groups compared totheir weight and/or volume. At the same time its compact structurecompared to the structure of linear polymers ensures desirableproperties like low viscosity and good admixing properties withthermoset plastics and thermoplastics. An example of anorganic/inorganic hybrid polymer with properties corresponding to ahyperbranched polymer is shown by Formula 3:

FORMULA 3

D = dendritic branching based on SiO_(1.5) T termination (functionalT-groups) D-groups that are bonded to fewer than three D units do notcarry hydrolysed and/or condensed substituents

Use of fat-soluble metal compounds in which the metal is present in itshighest stable oxidation state at standard conditions and/ororganic/inorganic hybrid polymers with properties similar tohyperbranched polymers can improve the compatibility between differentthermoplastics. In addition polymer compositions, e.g. in the form ofcompounds comprising at least one polyolefin and at least one of thefollowing components

-   -   a) a thermoplastic which is not a polyolefin,    -   b) hyperbranched organic/inorganic hybrid polymer comprising an        inorganic core carrying an organic branches, core and branches        forming a particle structure,    -   c) fat-soluble metal compound in which the metal is present in        its highest stable oxidation state at standard conditions        (25° C. and maximum 98% humidity)        in addition to known polymer additives (Hans Zweifel (ed.),        Plastics Additives Handbook, Carl Hanser Verlag, München,        (2001)) can be used in applications other than that of pure        thermoplastic materials including compositions thereof.        Objects

It is an object of the present invention to provide polymer compositionscomprising at least one polyolefin, for which properties like weatherresistance, scratch resistance, viscosity, degree of cross-linking,shelf life, barrier properties, flame and temperature resistance,rigidity, retention of additives and/r degradation products, andcontrolled release of additives easily can be adapted in dependence ofthe relevant application.

The Invention

The above mentioned objects are achieved by means of a polymercomposition as claimed in claim 1.

According to another aspect the invention concerns use of such a polymercompositions, as claimed in claims 17-19.

Preferred embodiments of the invention are disclosed by the dependentclaims.

The difference between the methods of manufacture of the polybranchedorganic/inorganic hybrid polymers defined by claims 2 and 12respectively solely depends on whether the starting organicamino-functional silanes used are hydrolysed and condensed or nothydrolysed. In the latter case hydrolysis and condensation form thefirst step in a process comprising at least two steps. In the formercase such a step obviously is redundant and therefore omitted. Theskilled artisan will furthermore understand that the group X—B is chosensuch that it will not be hydrolysed under the conditions that will beapplied for the method.

In either case free amine groups are modified through a chemicalsubstitution after the completed silane hydrolysis and condensation.Suitable chemical substitutions are conducted between the free aminegroups in the T groups and reactive compounds that preferably reactactually quantitatively with more or less free amine groups attemperatures typically below 470 K and pressures typically lower than0.3 MPa.

Particularly interesting are sol-gel processes by which the T groups maybe chemically modified in one or more steps immediately after thehydrolysis and condensation has been completed and for which the reactorequipment used for the silane hydrolysis and condensation may beemployed. Such batch processes form the basis for a very cost efficientmanufacture of particulate organic/inorganic polybranched polymers whichcan carry a large number of different T groups and which therefore maybe used in a large number of different industrial areas of application.

By reactions typical for primary and secondary amines is meant additionreactions, substitution reactions and combinations of such reactionswith suitable reactant such as, but not limited to, compounds comprisingepoxy groups, isocyanate groups, reactive double bonds, substitutablegroups, and proton donating groups.

By an alternative or supplementary modification an acid is added, whichmay be a Lewis acid or a Broensted acid, and which is able to cause anaddition to N atoms in the X—B group in order to convert such N atoms toquaternary nitronium ions.

By controlled hydrolysis and condensation in this description isunderstood hydrolysis and condensation of a silane compound as describedin WO publication No. 0208343 with the difference that the reactionmixture includes a suitable stabilizer that prevents oxidativedegradation of reactants and reaction products during hydrolysis andcondensation and subsequent modification.

The first step is hydrolysis of a suitable silane compound,R′—Si(OR)_(n), wherein the group R′ does not participate in thehydrolysis or condensation reactions. Alkoxide ligands are replaced byhydroxyl groups:Si—OR+H—OH Si—OH+ROH

A controlled amount of water and a controlled amount of a glycol basedsolvent is added during this step. The reaction temperature and thereaction time are also controlled.

The second step is condensation in which the hydroxyl group can reactwith hydroxyl groups or alkoxy groups from other silicon centres andform Si—O—Si bonds and water or alcohol respectively:Si—OH+HO—Si Si—O—Si+H₂OorSi—OR+HO—Si Si—O—Si+ROH

To manufacture particles of a certain size it is required to establishchemical conditions that ensures a correct balance between the kineticsof the two reactions, namely condensation and hydrolysis. While thecondensation contributes to formation of polymer chains from (single)monomer molecules, the hydrolysis contributes to a polycrystallinicprecipitation or oxohydroxide precipitation. The combination ofamino-functional silanes and exchange of alkoxide groups with strongligands will moderate the hydrolysis reaction, which will ensure thatthe polymer chains not become too long but remain in the size ofoligomers. In practice the particles will be prepared with a size of fewnanometers, more typically less than 10 nm. A suitable stabilizer isnormally added to the reaction composition to avoid oxidativedegradation of reactants and reaction products during hydrolysis andcondensation and subsequent modification. The resulting solution iscomprised of inorganic polymer particles dispersed in a solvent.

According to the present invention component d) of the composition maybe manufactured by a sol-gel process comprising at least two steps in adefined chronological sequence. In the first steps the core is preparedby controlled hydrolysis and condensation of a silane with formula:X—B—Si(—Y)₃with the provisions and definitions stated in claim 4.

In the second step the organic branches is developed by a substitutionof N—H hydrogen atoms of the X—B group through reactions that aretypical for primary and secondary amines and/or by the alternativemodification mentioned above. In the first mentioned type of reactionssuitable reactants are reactive compounds such as epoxides, cyclic andnon-cyclic acid derivatives, blocked and unblocked isocyanates,compounds with reactive double bonds, aldehydes, ketones, protondonating compounds, and compounds R—X that comprises

-   -   a) a suitable atom or atom group X and a group R,        in which R—X may react with more or less free amine groups in a        substitution reaction in which an atom or an atom group X is        replaced by an amine group (Endre Berner, “Laerebok i organisk        kjemi”, Aschehoug & Co., Oslo (1964), s. 144-147) and where the        group R is chosen among non-substituted saturated or unsaturated        C₁-C₂₄ alkyl, substituted saturated or unsaturated C₁-C₂₄ alkyl,        non-substituted or substituted aryl, aliphatic or aromatic        carbonyl, while the carbon chains of said compounds optionally        can contain one or more of the elements oxygen, nitrogen,        sulphur, phosphorous, silicon, and boron; or groups chosen among        condensation products or addition products of one or more types        of chemical compounds such as acids, alcohols, phenols, amines,        aldehydes, or epoxides in which the atom or atom group X        preferably is chosen among halogen, substituted or        non-substituted alkoxyl, phenoxyl, amine, carboxylate,        sulphonate, sulphinate, phosphonate, or phosphinate.

When step i) is an addition reaction it is convenient and preferred thatthis is conducted by substitution of the N—H hydrogen atom with ant A-=Bdouble bond where A, B are chosen among the elements C, O, N, S and P.According to an also preferred alternative the addition reactioninvolves ring opening of an epoxide group that optionally may besucceeded by reaction (substitution) with a ketone or an aldehyde. Yetanother preferred embodiment for the accomplishment of the additionreaction consists in a reaction at the N—H hydrogen atom with a blockedor unblocked isocyanate. Still another preferred embodiment foraccomplishing the addition reaction includes ring opening of a cyclicacid anhydride or derivative thereof, such as a carbonic acidderivative. Also a combination of such reactant as mentioned above maybe used for the desired addition reaction.

For some objects is preferred that the developed branches in theorganic/inorganic hybrid polymers includes groups that are derivativesof 2,2,6,6-tetramethylpiperidine or derivatives of phenol.

When using an addition reaction a molar excess of the reactant causingthe addition reaction may be added if desired, leading to repeatedaddition reactions which in practice involves a polymerization of theorganic branches.

As reactant when using at least one substitution reaction in step i) amono functional carboxylic acid or a derivative of a sulphinic orsulphonic acid may be used.

In step ii) the acid used can be a Lewis acid or a Broensted acid.

The method of manufacture according to the invention is not dependentupon a certain type of reaction medium and may be conducted in bothaqueous and organic based dispersion agents. It is particularlysurprising and beneficial that it is also applicable in water basedmedia, which is also environmentally favourable. Presence of theorganic/inorganic hybrid polymer may stabilize the polymer compositionand may act to cross-link polymer chains in the composition.

For particular purposes it is preferred to use particularly selectedreactants that lead to specific properties for the particulate,polybranched, organic/inorganic hybrid polymer. For example, in order toobtain a product with flame retardant properties it is advantageous touse reactants that comprise halogen for the reaction exemplified asaddition reaction or substitution reaction. If a particularlyhydrophobic end product is desired it may be advantageous to use atleast one fluorinated reactant in step i) and/or ii) of the methodaccording to the invention.

For further use or treatment of the particulate, polybranchedorganic/inorganic hybrid polymer it is convenient that it has at leastone polymerizable double bond, such as part of an acryl group, vinylgroup or an unsaturated fatty acid.

Examples of suitable epoxides for an addition reaction are monoglycidylcompounds that may be represented by:

where R₁ is chosen among groups like hydrogen, non-substituted saturatedor unsaturated C₁-C₂₄ alkyl, substituted saturated orunsaturated-C₁-C₂₄-alkyl, substituted or non-substituted aryl, aliphaticor aromatic carbonyl, in which the carbon chains of said compoundsoptionally may contain one or more of the elements oxygen, nitrogen,sulphur, phosphorous, silicon, and boron or where R₁ is chosen fromcondensation products or addition products of one or more type ofchemical compounds such as acids, alcohols, phenols, amines, aldehydesor epoxides.

Examples of suitable epoxides include compounds with epoxidized C═Cdouble bonds that may be represented by:

where R₁-R₄ are chosen among groups like hydrogen, non-substitutedsaturated or unsaturated C₁-C₂₄ alkyl, substituted saturated orunsaturated C₁-C₂₄ alkyl, substituted or non-substituted aryl, aliphaticor aromatic carbonyl, in which the carbon chains of said compoundsoptionally may contain one or more of the elements oxygen, nitrogen,sulphur, phosphorous, silicon, and boron or where R₁ is chosen fromcondensation products or addition products of one or more type ofchemical compounds such as acids, alcohols, phenols, amines, aldehydesor epoxides.

Examples of reactive double bonds are A=B double bonds where A, B arechosen among the elements C, O, N, S and P.

Examples of acid derivatives are:

Derivatives of carboxylic acids

Derivatives of suiphonic acids

Derivatives of suiphinic acids

Cyclic acid derivatives n = 0–10 Y = O, S, N—R₁

Carbonic acid derivatives Y = O, S, N—R₁, Z = O, S, N—R₁

Cyclic acid anhydrides and corresponding derivatives n = 0–10 Y = O, S,N—R₁

Cyclic carbonic acid derivatives n = 0–10 Y = O, S, N—R₁, Z = O, S, N—R₁

Where R₁ is chosen among groups like hydrogen, non-substituted saturatedor unsaturated C₁-C₂₄ alkyl, substituted saturated or unsaturated C₁-C₂₄alkyl, substituted or non-substituted aryl, aliphatic or aromaticcarbonyl, in which the carbon chains of said compounds optionally maycontain one or more of the elements oxygen, nitrogen, sulphur,phosphorous, silicon, and boron or where R₁ is chosen from condensationproducts or addition products of one or more type of chemical compoundssuch as acids, alcohols, phenols, amines, aldehydes or epoxides and X isa suitable exit group such as halogen, substituted or non-substitutedalkoxy, phenoxy, amine, carboxylate, sulphonate, sulphinate,phosphonate, or phosfinate.

Examples of suitable isocyanates may be represented by:

Where R₁ is chosen among groups like hydrogen, non-substituted saturatedor unsaturated C₁-C₂₄ alkyl, substituted saturated or unsaturated C₁-C₂₄alkyl, substituted or non-substituted aryl, aliphatic or aromaticcarbonyl, in which the carbon chains of said compounds optionally maycontain one or more of the elements oxygen, nitrogen, sulphur,phosphorous, silicon, and boron or where R₁ is chosen from condensationproducts or addition products of one or more type of chemical compoundssuch as acids, alcohols, phenols, amines, aldehydes or epoxides andwhere the isocyanate group my be blocked by means of known chemicalsubstances.

Examples of suitable aldehydes and ketones may be represented by:

Where R₁ is chosen among groups like hydrogen, non-substituted saturatedor unsaturated C₁-C₂₄ alkyl, substituted saturated or unsaturated C₁-C₂₄alkyl, substituted or non-substituted aryl, aliphatic or aromaticcarbonyl, in which the carbon chains of said compounds optionally maycontain one or more of the elements oxygen, nitrogen, sulphur,phosphorous, silicon, and boron or where R₁ is chosen from condensationproducts or addition products of one or more type of chemical compoundssuch as acids, alcohols, phenols, amines, aldehydes or epoxides.

An example of a combination of reactions is

-   -   a) substitution of N—H hydrogen atoms at the non-hydrolyzable        substituent X—B group by an epoxide, resulting in the formation        of an aminoalcohol,    -   b) substitution of the aminoalcohol by a ketone or an aldehyde        resulting in the formation of an oxazolidine.

In the manufacture of a polybranched, organic/inorganic hybrid polymerby a sol-gel process, the hybrid polymer having the form of an inorganiccore and organic branches, a suitable stabilizer is normally added tothe reaction composition to prevent oxidative degradation of thereactants and reaction products during hydrolysis and condensation andsubsequent modification of X—B—Si(—Y)₃. Suitable stabilizers are radicalscavengers based on hindered amines, one or more antioxidants or acombination of same (Hans Zweifel (ed.), Plastics Additives Handbook,Carl Hanser Verlag, München, (2001), 10-19).

By first hydrolysing the molecules that comprises the organic core andthereafter through suitable reaction, addition or addition, attach theorganic branches thereto, the method of the present invention therebyprovides a particularly high degree of branching and a control of theparticle size in the thus produced sol that has never before beenachieved. This leads to several advantages. Firstly the hydrolysis maybe conducted more completely than what is the case if the particlecomposition includes some very large particles. Secondly the risk thatwater used for the hydrolysis to some extent unintentionally reacts withactive groups in the organic parts of the molecule is avoided.

The invention thus provide a possibility of manufacturing a large numberof differently functionalized organic/inorganic hybrid polymers withproperties corresponding to the properties of hyperbranched polymers,through a simple two step batch process under mild conditions (T<470 Kand pressure P<0.3 MPa).

Such organic/inorganic hybrid polymers have properties that arecomparable with the properties of organic, hyperbranched polymers andmay be used for many applications, like functional additives inthermoplastics and thermoset plastics, e.g. as antioxidant, UV absorb orradical scavenger, as cross-binder in thermoplastics and thermosetplastics, as component in adhesives, lacquers and coating products andas functional material in other connections. Used as additive thepolybranched hybrid polymers prepared according to the inventioncontribute to a lasting increase in scratch resistance and weatherresistance for the products in which they are used.

Temperature and stability during hydrolysis of the organic/inorganichybrid polymers according to the invention are better than those of theorganic hyperbranched polymers due to stable Si—O bonds in the polymercore and due to the core's compact structure with a very high degree ofcross-linking.

Reversible viscosity changes is observed during heating/cooling due tothe particulate structure with a stable inorganic core and functioncarrying organic groups that are bonded to the inorganic core, which isimportant in connection with the subsequent treatment/processing ofproducts based on the invention.

The choice of method for the manufacture of materials and productsaccording to the invention enables an industrial utilization of theinvention in a cost efficient manner. The manufacture of materials andproducts according to the invention is based on a batch process undermild conditions (T<470 K and pressure P<0.3 MPa) in which the rawmaterials are chosen among a definite group of inexpensive silanes andbulk chemicals that are used in large quantities in industrialutilizations of polymers

By convenient choice of raw materials for the method according to theinvention, stabilizers, coating forming additives or other additives maybe manufactured. Such stabilizers or other additives provide a broaderrange of applications than what is the case for known, mono functionalstabilizers and may be used in lacquers, paints, thermoset plastics andthermoplastics. By convenient choice of raw materials one may forinstance in combination with a suitable polymer achieve an excellentbarrier layer for molecules in gas and liquid form, like water, O₂, CO₂and hydrocarbons.

The invention furthermore concerns additives for avoiding leakages ofadditives and/or degradation products. Correspondingly self-organizingnetworks may be formed, such as in adhesives orthermo-stable/thermo-reversible networks that find use in functionalmaterials.

Fat-soluble metal compounds for use in a composition according to theinvention may be prepared (manufactured) by reacting a metal salt withan acidic, organic compound in a process in which a suitable oxidationagent ensures that all the metal in the end product is present in itshighest stable oxidation step at standard conditions (25 C and maximum98% humidity). The acidic, organic compound can e.g. be a C₈-C₂₄ fattyacid or a C₈-C₂₄ fatty acid derivative. A particular feature of themanufacturing process can involve the use of a completely or partiallyhalogenated C₈-C₂₄ fatty acid or derivative thereof. Another particularfeature of the manufacturing process can be that the C₈-C₂₄ fatty acidor C₈-C₂₄ fatty acid derivative is completely or partially unsaturated.A third particular feature of the manufacturing process can be that theoxidation agent used is hydrogen peroxide or an organic peroxide.

Per se known polymer additives are described by Hans Zweifel (HansZweifel (ed.), Plastics Additives Handbook, Carl Hanser Verlag, München,(2001)).

The polymer composition according to the invention may have the form ofan independent, homogenous product, i.e. that all the components areevenly distributed in a polymer matrix. The polymer composition may alsoconstitute a layer of a laminate in which the other layers may have acomposition that either fall within or not fall within the definition ofthe polymer composition according to the invention. In cases where theother layers do not fall within the definition according to theinvention, these layers may be polymers of one or more components orsubstrates of another type, i.e. not polymers. The polymer compositionmay also have the form of a tube that either is a complete product orconstitutes a protecting film around other components that similar tothe layers of the laminate structure either may fall within or not fallwithin the definition of the polymer composition according to thepresent invention.

With “partially heterogeneous structure” inn this context is understooda product that does not have a uniform structure throughout but may havea composition in the form of a laminate in which each layer ishomogenous but different from the composition of at least one otherlayer.

The polymer composition may, however, also have a heterogeneousstructure (product) in which each layer separately do not fall withinthe definition of the present invention, but where the product as awhole still falls within the definition of the product. For example,component d) and e) may constitute a majority of one layer of theproduct while another layer of the product may be a pure polymer such asPE or PP.

A polymer composition according to the invention may be used as atransition (intermediate) layer between a coating based on apolybranched organic/inorganic hybrid polymer and a thermoplastic(material).

EXAMPLES Experiment 1

Manufacture of a polybranched organic/inorganic hybrid polymer by asol-gel process.

-   -   a) 221.4 g (1.00 mol) γ-aminopropyltriethoxysilane (A-1100, GE        Silicones, USA) was placed in a 1000 ml round bottom flask with        hose cooler and magnetic stirrer. A mixture of 93.6 g (0.60        moles) butyldiglycol (BDG) and 22.5 g (1.30 moles) water and        1.00 g Tinuvin 123 (Ciba Specialty Chemicals, Switzerland) was        added. The mixture was heated in an oil bath at 110° C. under        reflux for 45 minutes. Thereafter the volatile reaction products        or reactants were removed in a vacuum distillation at the oil        bath temperature of 110° C.-160° C. and a vacuum gradient from        about 1000 mbar to less than 20 mbar. The distillation was        terminated when the pressure in the round bottom flask has        reached 20 mbar or less for 10 minutes. Ca. 192 ml distillate        was recovered. The reaction product was a clear, uncoloured        liquid with a Gardner Color=1 (according to. Gardner Color        Scale/ASTM D1544)    -   b) The reaction product from a) was heated to 70° C. to obtain a        clear liquid. Then 256.4 g (1.00 moles) of Araldite DY-E        (glycidylether of C₁₂-C₁₄-alcohol, Vantico AG (Huntsman AG),        Switzerland) was added and the reaction mixture was held at        70° C. for an hour. A clear product with a Gardner Color=1,        having the form of a viscous gel at 20° C. and a non-viscous        liquid at 90° C., was obtained.

The distillate in a) comprises insignificant amounts of volatile amine.In a corresponding experiment in which no stabilizer (like e.g. Tinuvin123) was used during the manufacturing process, the distillate in a)comprises relatively large amounts of the volatile amine products, whichmainly is due to degradation of A-1100 during the synthesis.

Experiments 2-7

The manufacture of a polybranched organic/inorganic hybrid polymer by asol-gel process like under experiment 1, but with use of other epoxidecompounds or a mixture of epoxide compounds in step b). The followingproducts were prepared:

Gardner- Experiment # Silane Epoxide 1 Epoxide 2 Colour Experiment 2A-1100 Araldite DY-E — 1 (512.8 g; 2.00 moles) Experiment 3 A-1100Araldite DY-K — 1-2 (164.2 g; 1.00 moles) Experiment 4 A-1100 BGE — 1(130.2 g; 1.00 moles) Experiment 5 A-1100 BGE Araldite DY-K 1 (65.1 g;(82.1 g; 0.50 moles) 0.50 moles) Experiment 6 A-1100 BGE MGE 1 (65.1 g;(71.1 g; 0.50 moles) 0.50 moles) Experiment 7 A-1100 BGE FGE 2 (65.1 g;(77.1 g; 0.50 moles) 0.50 moles) BGE = tert-butylglycidylether, CAS[7665-72-7], Sigma-Aldrich Norway AS MGE = Glycidylmethacrylate, CAS[106-91-2], Sigma-Aldrich Norway AS, stabilized with addition of 0.2%antioxidant hydroquinin monomethylether CAS [150-76-5], Sigma-AldrichNorway AS Araldite DY-K = glycidyl-2-methylphenylether, CAS [2210-79-9],Huntsman AG, Switzerland FGE = furfurylglycidylether, CAS [5380-87-0],Sigma-Aldrich Norway ASAll products were viscous gels at 20° C. and non-viscous liquids at 90°C.

Experiment 8

Comparison example to Example 5 in which a bifunctional epoxide is usedas epoxide 2:

Gardner- Experiment nr. silane Epoxide 1 Epoxide 2 Color Experiment 8A-1100 BGE Araldite DY-C 1 (65.1 g; (128.2 g; 0.50 moles) 0.50 moles)Araldite DY-C = 1,4-Bis(2,3-epoxypropoxy)-methylcyclohexane, HuntsmanAG, Switzerland.

The product was a clear gel that does not become less viscous whenheated. At 200° C. the product starts to degrade with no apparentviscositu change.

Experiment 9

Comparison experiment to Experiment 3, in which step b) was conductedprior to step a):

Gardner- Experiment nr. Silane Epoxide 1 Epoxide 2 Color Experiment 9A-1100 Araldite DY-K — 4-5 (164.2 g; 1.00 moles)

The product was a clear gel but had much stronger colour than theproduct of Experiment 3.

Experiment 10

The manufacture of a polybranched, organic/inorganic hybrid polymer by asol-gel process while also including an UV absorber during themanufacture:

-   -   a) 221.4 g (1.00 moles) of γ-aminopropyltriethoxysilane (A-1100,        GE Silicones, USA) was placed in a 1000 ml round bottom flask        with hose cooler and magnetic stirrer. A mixture of 93.6 g (0.60        moles) butyldiglycol (BDG) and 22.5 g (1.30 moles) of water and        1.00 g Tinuvin 123 (Ciba Specialty Chemicals, Switzerland) was        added. The mixture was heated in an oil bath at 110° C. under        reflux for 45 minutes. To the still warm reaction product a        heated solution of 12.0 g Cyasorb UV-1164 (Cytec Inc., USA)        dissolved in 36 ml toluene, was added. Thereafter the volatile        reaction products or reactants were removed in a vacuum        distillation at the oil bath temperature of 110° C.-160° C. and        a vacuum gradient from about 1000 mbar to less than 20 mbar. The        distillation was terminated when the pressure in the round        bottom flask has reached 20 mbar or less for 10 minutes. Ca. 226        ml distillate was recovered. The reaction product was a clear        liquid with a Gardner Colour=3 (according to. Gardner Colour        Scale/ASTM D1544).

The reaction product from a) was heated to 70° C. to obtain a clearliquid. Then 512.8 g (1.00 mol) Araldite DY-E (glycidylether ofC₁₂-C₁₄-alcohol, Vantico AG (Huntsman AG), Switzerland) was added andthe reaction mixture was held at 70° C. for an hour. The obtainedproduct was clear with a Gardner Color=3, which is a viscous gel at 20°C. and a non-viscous liquid at 90° C. AT 20° C. the product after a fewhours shows sign of crystallization. The product again became clear andnon-viscous when reheated to 70° C.

Experiment 11

Manufacture of polybranched, organic/inorganic hybrid polymer by asol-gel process followed by a two step modification:

-   -   a) 221.4 g (1.00 mol) of γ-aminopropyltriethoxysilane (A-1100,        Crompton Corporation (GE Plastics), USA) is placed in a 1000 ml        round bottom flask with hose cooler and magnetic stirrer. A        mixture of 93.6 g (0.60 moles) of butyldiglycol (BDG) and 22.5 g        (1.30 moles) of water and 1.00 g Tinuvin 123 (Ciba Specialty        Chemicals, Switzerland) was added. The mixture was heated in an        oil bath at 110° C. under reflux for 45 minutes. Then volatile        reaction products or reactants were removed in a vacuum        distillation at the oil bath temperature of 110° C.-160° C. and        a vacuum gradient from about 1000 mbar to less than 20 mbar. The        distillation was terminated when the pressure in the round        bottom flask has reached 20 mbar or less for 10 minutes. Ca. 192        ml of distillate was recovered. The reaction product was a        clear, uncoloured liquid with a Gardner Color=1 (according to.        Gardner Color Scale/ASTM D1544).    -   b) The reaction product from a) was heated to 70° C. to obtain a        clear liquid. Then 130.2 g (1.00 moles) of        tert-butylglycidylether was added and the reaction mixture was        held at 70° C. for an hour. A solution of 98.1 g (1.00 moles) of        cyclohexanone in 100 ml of toluene was added. The reaction        mixture was boiled with reflux for 15 minutes and thereafter the        volatile reaction products or reactants were removed by vacuum        distillation. A clear product with a Gardner Colour=2 was        obtain, having the form of a viscous gel at 20° C. and a        non-viscous liquid at 90° C.

Experiment 12

In a manner corresponding to Experiment 11 a polybranchedorganic/inorganic hybrid polymer with functional groups of the typehindered amine was prepared from triacetoneamine(2,2,6,6-tetramethyl-4-piperidinone, CAS [826-36-8], Sigma-AldrichNorway AS).

Experiment 13

In a manner corresponding to Experiment 11 a polybranchedorganic/inorganic hybrid polymer with functional groups of phenolic typewas prepared from 3-hydroxybenzaldehyde, CAS [100-83-4], Sigma-AldrichNorway AS)

Experiment 14

Manufacture of polybranched, organic/inorganic hybrid polymer by asol-gel process using an ester.

-   -   a) 221.4 g (1.00 mol) of γ-aminopropyltriethoxysilane (A-100,        Crompton Corporation (GE Plastics), USA) was placed in a 1000 ml        round bottom flask with hose cooler and magnetic stirrer. A        mixture of 93.6 g (0.60 moles) of butyldiglycol (BDG) and 22.5 g        (1.30 moles) of water and 1.00 g of the product from Experiment        12 was added. The mixture was heated in an oil bath at 110° C.        under reflux for 45 minutes. Then volatile reaction products or        reactants were removed in a vacuum distillation at the oil bath        temperature of 110° C.-160° C. and a vacuum gradient from about        1000 mbar to less than 20 mbar. The distillation was terminated        when the pressure in the round bottom flask has reached 20 mbar        or less for 10 minutes. Ca. 192 ml of distillate was recovered.        The reaction product was a clear, uncoloured liquid with a        Gardner Color=1 (according to. Gardner Color Scale/ASTM D1544).    -   b) The reaction product from a) was heated to 70° C. to obtain a        clear liquid. Then 136.2 g (1.00 mole) of methylbenzoate (CAS        [93-58-3], Sigma-Aldrich Norway AS) and 0.5 g of acetic        anhydride (CAS [108-24-7], Sigma-Aldrich Norway AS) in 150 ml        toluene was added and the reaction mixture was boiled with        reflux for an hour. Then volatile reaction products or reactants        were removed in a vacuum distillation. The reaction product was        a clear, and had a Gardner Colour=1, having the form of a        viscous gel at 20° C. and a non-viscous liquid at 90° C.

Experiment 15

Manufacture of polybranched, organic/inorganic hybrid polymer by asol-gel process using an isocyanate.

-   -   a) 221.4 g (1.00 mol) of γ-aminopropyltriethoxysilane (A-1100,        Crompton Corporation (GE Plastics), USA) was placed in a 1000 ml        round bottom flask with hose cooler and magnetic stirrer. A        mixture of 93.6 g (0.60 moles) of butyldiglycol (BDG) and 22.5 g        (1.30 moles) of water and 1.00 g of the product from Experiment        12 was added. The mixture was heated in an oil bath at 110° C.        under reflux for 45 minutes. Then the volatile reaction products        or reactants were removed in a vacuum distillation at the oil        bath temperature of 110° C.-160° C. and a vacuum gradient from        about 1000 mbar to less than 20 mbar. The distillation was        terminated when the pressure in the round bottom flask has        reached 20 mbar or less for 10 minutes. Ca. 192 ml of distillate        was recovered. The reaction product was a clear, uncoloured        liquid with a Gardner Colour=1 (according to. Gardner Color        Scale/ASTM D1544).    -   b) The reaction product from a) was heated to 70° C. to obtain a        clear liquid. Then 155.4 g (1.00 mole) of octylisocyanate (CAS        [3158-26-7], Sigma-Aldrich Norway AS) was added and the reaction        mixture was held at 70° C. for an hour. A product is obtained        which is white and waxy at 20° C. and which is a non-viscous        liquid with a Gardner Color=1 at 90° C.

Experiment 16

The product from Experiment 6 is applied to a plasma treatedpolyethylene sheet (Borealis AS, Norway) and cured by heating the sheetwith the product applied from Experiment 5 to 160° C. for 2 hours and80° C. for 16 hours. A continuous coating with a good adhesion to thepolyolefinic surface is formed. The coating is not dissolved from thepolyolefinic surface when left in xylene in 180 hours at 40° C.

Experiment 17

The products from Experiment 1, 2 and 12 were compounded into apolypropylene homo polymer (HG430MO, Borealis AS) by means of a Clextralspecially instrumented double helix extruder. The amount ofpolybranched, organic/inorganic hybrid polymer was 5% in all cases. Thecompounded products were injection moulded by means of a Battenfeldinjection moulding apparatus to sample rods according to ASTM D3641. Thesample rods were homogenous and about as transparent as injectionmoulded polypropylene homo polymer without polybranched,organic/inorganic hybrid polymer.

Experiment 18

The viscosity of the product from Experiment 12 was measured in arheometer of the type Physika MCR 300 at 20° C. og 90° C. Themeasurements were conducted three times for each sample and the meanvalue at each temperature was calculated. The result is shown in thetable below. For comparison the viscosity of the POSS compoundIsooctyl-POSS (cage mixture; Sigma-Aldrich Norway AS, ref.-nr. 560383)was also measured. The table also shows the viscosity values forn-butanol at the same temperatures (Handbook of Chemistry and Physics,CRC Press, 71. ed., (1990-1991)).

Viscosity at Viscosity at Compound 20° C. [mPa*s] 90° C. [mPa*s]Experiment 12 800 000 800 POSS  16 000 200 n-butanol    3 ~0.7

The relative change in viscosity shown for the result of Experiment 12(according to the invention) is of a factor 1000 while it for thecomparison examples is of a factor 80 (POSS) and less than 5(n-butanol).

Experiment 19

Sample rods for testing as prepared in Experiment 17 and comprisingpolybranched, organic/inorganic hybrid polymer prepared in Experiment 1,were tested for tensile strength according to ASTM D638. The resultsfrom these tests are characterized by the samples' E module [MPa],maximum tensile strength [MPa] and break elongation [%]. Table 5 andtable 6 show the results of the tensile strength testing.

Polymer composition 1 corresponds to a pure homo polymer of the typeHG430MO (Borealis AS, Norway).

Polymer composition 2 was comprised by 90% PP-homo polymer of the typeHG430MO and 10% polybranched organic/inorganic hybrid polymer asmanufactured in Experiment 1. The sample rods were cooled to 25° C.immediately after the injection moulding.

Polymer composition 3 was comprised by 90% PP-homo polymer of the typeHG430MO and 10% polybranched organic/inorganic hybrid polymer asmanufactured in Experiment 1. After the injection moulding the samplerods were post-cured at 130° C. for an hour before being cooled to 25°C.

Polymer Break composition E-module Maximum tensile elongation No. [MPa]strength [MPa] [%] 1 1550 34.5 <20 2 1115 ± 74 26.2 ± 0.3 258 ± 123 31319 ± 77 27.7 ± 0.6 163 ± 38 

The results in the table show that the polymer composition according tothe invention compared to pure thermoplastic materials can have asubstantially improved elongation of break, while the reduction ofmaximum tensile strength is acceptable.

Experiment 20

Manufacture of a fat-soluble ferric compound (“Nor-X”).

The synthesis was conducted in a heatable 5 liter glass reactor withfeeding funnels, a mechanically operated glass stirrer, a glass mantledthermometer, a distillation cooler, an adjustable air inlet and a bottomvalve. 2.180 kg (7.66 moles) of stearic acid was melted in the reactor.The air inlet was adjusted to about 200 ml air per minute and thetemperature in the reactor was controlled to 120° C. 600 grams (2.22moles) of ferric chloride hexahydrate was dissolved in 600 ml of waterto obtain about 900 ml of an aqueous ferric chloride solution. Thissolution was added through one of the feeding funnels at a rate of about20 ml per minute to the melted stearic acid. The total addition ofaqueous ferric chloride solution was controlled to ensure that theamount of distilled water and hydrogen chloride corresponded to theamount aqueous ferric chloride solution added. Continuous addition ofair and a 2 ml per minute addition of a 3% aqueous hydrogen peroxidesolution through the other feeding funnel ensured that oxidation stateIII of the ferric ions were maintained. After completed addition ofaqueous ferric chloride solution the mixture was boiled and distilledunder continuous addition of air and a 5 ml per minute addition of a 3%aqueous hydrogen peroxide solution until the distinct yellow colour ofaqueous ferric chloride solution no longer could be observed. Then theferric stearate product was drained through the bottom valve into 10liter of aqueous hydrogen peroxide solution. When the following gasdevelopment is about to terminate the ferric stearate product isfiltered from the liquid phase and thoroughly washed with water toremove any remains of ferric chloride. The ferric stearate product isthen dispersed in a 1% aqueous hydrogen peroxide solution at 55 C for 2hours by means of a dispersing rod. The dispersed ferric stearateproduct is filtered from the liquid phase, thoroughly washed with waterand dried in a convection oven at 50° C.

Experiment 21

Polymer composition based on PP homo polymers (HG430MO), LLDPE (Exact0230, Exxon), polybranched organic/inorganic hybrid polymer asmanufactured in Experiment 2, fat-soluble ferric compound (“Nor-X”, cf.Exp. 20) and a stabilizing composition (50% Irgafos 168, Ciba SpecialtyChemicals and 50% Cyasorb UV-2908, Cytec).

The table below shows that polymer compositions according to the presentinvention can exhibit properties of materials that are superior to theproperties of the thermoplastic materials employed.

Exp. Stabi- Yield Break PP LLDPE 2 lizer “Nor-X” stress elongation # [%][%] [%] [ppm] [%] [MPa] [%] 0 100 0 0 0 0 38.1 ± 1.0 14 ± 10 1 93 0 7 00 35.8 ± 0.6 52 ± 45 2 67.9 26.8 5.1 500 0.2 22.2 ± 0.3 558 ± 162 3 67.926.4 5.1 500 0.6 22.9 ± 0.4 493 ± 106 4 67.9 26.4 5.1 0 0.6 23.4 ± 0.2577 ± 127

Experiment 22

Polymer compositions based on PP-homo polymer (HG125MO, Borealis), LLDPE(FG5190, Borealis), and fat-soluble ferric compound (“Nor-X”, Experiment20) were prepared by extrusion in a Clextral specially instrumenteddouble helix extruder. Polymer compounds were injection moulded by meansof a Battenfeld injection moulding machine to test rods according toASTM D3641. The test rods were tested for tensile strength according toASTM D638. The results from the tenile strength tests are defined by Emodule [MPa], maximum tensile strength [MPa] and break elongation [%] inthe table below.

Amount Break PP Amount Nor-X E-module Yield stress elongation MFI [10g/min] [%] [%] [MPa] [MPa] [%] 190° C./2.16 kg 100 0 1550* 34.5* <20 5.490 0 1592 ± 126 33.1 ± 0.3  448 ± 128 2.5 80 0 1373 ± 102 30.7 ± 0.3 552± 48 4.2 60 0 1104 ± 158 25.4 ± 0.4  524 ± 119 3.1 40 0 623 ± 65 18.3 ±0.2 416 ± 11 1.9 20 0 303 ± 20 14.9 ± 1   319 ± 24 1.4 0 0 170-210* 12*74O-850* 1.0 90 0.5  836 ± 103 31.6 ± 0.2 631 ± 98 6.9 80 0.5  755 ± 12029.5 ± 0.1 573 ± 96 6.0 60 0.5 642 ± 57 24.9 ± 1.2 468 ± 3  4.5 40 0.5642 ± 31 25.2 ± 0.8 467 ± 28 4.3 20 0.5 328 ± 27 14.4 ± 0.5 556 ± 16 1.4

The results show that fat-soluble iron products as prepared byExperiment 20 (Nor-X) may be suitable as compatibilizer for PP/LLDPE.Polymer compositions in the table above with 0.5% fat-soluble ferricproduct (“Nor-X”) showed excellent properties in foil blowing, which wasnot the case for most of the polymer compositions without “Nor-X”.

Experiment 23

2824 g (12.8 moles) of γ-aminopropyltriethoxysilane (DYNASYLAN® AMEO,Degussa AG, Germany) was placed in a 5 liter reactor (NORMAG Labor-undProzesstechnik, Ilmenau, Germany) with temperature controlled heatmantle, stirring assembly, thermometer, dropping funnel, vertical coolerwith column head for rapid change between reflux and distillation andvaccuum connection (membrane pump). A mixture of 1241 g (7.7 moles) ofbutyldiglycol (BDG) and 298 g (16.6 moles) of water and 20 mg of(2,2,6,6-tetrametyl-4-piperidinon, CAS [2564-83-2], Sigma-Aldrich NorwayAS). The mixture was heated with reflux for 45 minutes. Then volatilereaction products or reactants were removed in a vacuum distillation atthe oil bath temperature of 110° C.-160° C. and a vacuum gradient fromabout 1000 mbar to less than 20 mbar. The distillation was terminatedwhen the pressure in the round bottom flask has reached 20 mbar or lessfor 10 minutes. Ca. 2690 ml of distillate was recovered. The reactionproduct was a clear, colourless liquid with Gardner Color=1 (accordingto Gardner Color Scale/ASTM D1544).

Experiment 24

Manufacture of polybranched, organic/inorganic hybrid polymer by asol-gel process in a 5 liter reactor.

-   -   2801 g (12.7 moles) of γ-aminopropyltriethoxysilane (DYNASYLAN®        AMEO, Degussa AG, Germany) was placed in a 5 liter reactor        (NORMAG Labor-und Prozesstechnik, Ilmenau, Germany) with        temperature controlled heat mantle, stirring assembly,        thermometer, dropping funnel, vertical cooler with column head        for rapid change between reflux and distillation and vacuum        connection (membrane pump). A mixture of 821 g (7.6 moles) of        2-butoxyethanol (DOWANOL EB, Dow Chemical, USA) and 296 g (16.4        moles) of water and 16 mg of the reaction product of        Experiment 12. The mixture was heated under reflux for 45        minutes. Then the volatile reaction products or reactants were        removed in a vacuum distillation at the oil bath temperature of        110° C.-160° C. and a vacuum gradient from about 1000 mbar to        less than 20 mbar. The distillation was terminated when the        pressure in the round bottom flask has reached 20 mbar or less        for 10 minutes. Ca. 2334 ml of distillate was recovered. The        reaction product was a clear, uncoloured liquid with a Gardner        Color=1 (according to Gardner Color Scale/ASTM D1544).    -   Available NH activity of the product was determined by complete        reaction with tert-butylglycidylether (BGE). Excess BGE was        removed by vacuum distillation. The manufactured product showed        an available NH activity (“epoxy number”) of 70 grams per epoxy        equivalent.

Experiment 25

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   a) 558 g of the reaction product from Experiment 24 was heated        to 70° C. Then 625 g (4.8 moles) of tert-butylglycidylether        (BGE) and the reaction mixture was heated to 100° C. The        reaction is strongly exothermic and by means of the controllable        heat mantle was ensured that the temperature in the reaction        mixture did not exceed 160° C. The reaction mixture was cooled        to 80° C.    -   b) A hot solution of 621 g triacetoneamine (TAA) in 552 g        toluene was added. The reaction mixture was heated under reflux        for 20 minutes. Thereafter an azeotrope of toluene and water was        distilled off, ca. 610 g. The procedure was terminated with        vacuum distillation at 20 mbar or less and a temperature in the        reaction mixture of 160° C. A brownish, yet clear product was        obtained which was a viscous gel at 20° C. and a non-viscous        liquid at 90° C.

Experiment 26

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   a) 551 g of the reaction product from Experiment 24 was heated        to 70° C. Then 1460 g (5.7 moles) of Araldite DY-E        (glycidylether of C₁₂-C₁₄-alcohol, Huntsman AG, Switzerland) was        added and the reaction mixture was heated to 100° C. The        reaction is strongly exothermic and by means of the controllable        heat mantle was ensured that the temperature in the reaction        mixture did not exceed 160° C. The reaction mixture was cooled        to 80° C.    -   b) 160 g of a hot solution of Campher (CAS [76-22-2],        Sigma-Aldrich Norway AS) in 280 g hexane was added. The reaction        mixture was heated under reflux for 20 minutes. Thereafter an        azeotrope of hexane and water was distilled off, ca. 290 g. The        procedure was terminated with vacuum distillation at 20 mbar or        less and a temperature in the reaction mixture of 160° C. A        product was obtained which was a clear viscous gel at 20° C. and        a clear non-viscous liquid at 90° C.

Experiment 27

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   480 g of the reaction product from Experiment 24 was heated to        80° C. Then 1562 g (12.0 moles) of tert-butylglycidylether (BGE)        was added and the reaction mixture was heated to 100° C. The        reaction is strongly exothermic and by means of the controllable        heat mantle was ensured that the temperature in the reaction        mixture did not exceed 160° C. The procedure was terminated with        vacuum distillation at 20 mbar or less and a temperature in the        reaction mixture of 160° C. A yellowish, yet clear product was        obtained which was a strongly viscous gel at 20° C. and a        non-viscous liquid at 140° C.

Experiment 28

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   140 g of the reaction product from Experiment 24 was heated to        70° C. Then 466 g (4.1 moles) of ε-caprolactone (CAS [502-44-3],        Sigma-Aldrich Norway AS) was added and the reaction mixture was        heated to 100° C. Two hours later 627 g of Araldite DY-E        (glycidylether of C₁₂-C₁₄-alcohol, Huntsman AG, Switzerland) was        added and the reaction mixture was heated to 160° C. The        procedure was terminated with vacuum distillation at 20 mbar or        less and a temperature in the reaction mixture of 160° C. 210 g        of a distillate was distilled out. A clear gel which was viscous        at 20° C. and non-viscous (liquid) at 90° C. was obtained.

Experiment 29

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   70 g of the reaction product from Experiment 24 was heated under        agitation in a borosilicate glass flask (Schott AG, Germany) by        means of a water bath to 70° C. Then 171 g (1.5 moles) of        ε-caprolactone (CAS [502-44-3], Sigma-Aldrich Norway AS) was        added and the reaction mixture was heated to 90° C. Two hours        later 154 g Araldite DY-E (glycidylether of C₁₂-C₁₄-alcohol,        Huntsman AG, Switzerland) was added and the reaction mixture was        held at 90° C. for four hours under agitation. Thereafter the        reaction mixture was agitated at 40° C. for a week. A clear gel        which was viscous at 20° C. and non-viscous (liquid) at 90° C.        was obtained.

Experiment 30

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   28 g of the reaction product from Experiment 24 was heated under        agitation in a borosilicate glass flask (Schott AG, Germany) by        means of a water bath to 70° C. Then 137 g (1.5 moles) of        ε-caprolactone (CAS [502-44-3], Sigma-Aldrich Norway AS) was        added and the reaction mixture was heated to 90° C. Two hours        later 57 g oleic acid (CAS [112-80-1], Sigma-Aldrich Norway AS)        was added and the reaction mixture was agitated at 40° C. for 16        hours. A clear gel which was viscous at 20° C. and non-viscous        (liquid) at 90° C. was obtained.

Experiment 31

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   35 g of the reaction product from Experiment 24 was placed in a        borosilicate glass flask (Schott AG, Germany). While agitating        31 g propylenecarbonate (Huntsman AG, Switzerland) was added and        the reaction mixture was agitated at ambient temperature. The        reaction is strongly exothermic and a clear gel which is viscous        at 20° C. and non-viscous (liquid) at 120° C. was obtained.

Experiment 32

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   14.0 g of the reaction product from Experiment 24 was placed in        a borosilicate glass flask (Schott AG, Germany). Then 12.3 g        propylenecarbonate (Huntsman AG, Switzerland) was added under        agitation and the reaction mixture was agitated at ambient        temperature. The reaction is strongly exothermic and a clear gel        which is viscous at 20° C. and non-viscous (liquid) at 120° C.        was obtained. 34 l of a lacquer (SZ-006, Rhenania GmbH, Germany)        was added. The composition was agitated at 40° C. for 40 hours.        A modified lacquer was obtained which had approximately the same        shelf-life as the original lacquer.

Experiment 33

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   14 g of the reaction product from Experiment 24 was placed in a        borosilicate glass flask (Schott AG, Germany). Then 49 g of        Araldite DY-P (p-tert-butylphenylglycidyleter, Huntsman AG,        Switzerland) was added under agitation and the reaction mixture        was agitated at ambient temperature. The reaction is strongly        exothermic and a clear gel which is viscous at 20° C. and        non-viscous (liquid) at 120° C. was obtained.

Experiment 34

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   15.4 g of the reaction product from Experiment 24 was dispersed        in 40 g of water and placed in a borosilicate glass flask        (Schott AG, Germany). The dispersion was agitated at 40° C. for        two hours and thereafter filtered, first through a filter paper        and then through a teflon membrane filter (pore size 0.45 μm).        The filtrate was placed in another borosilicate flask and heated        to 40° C. Then a mixture of 23 g of glycidylmethacrylate and 8 g        butoxyethanol was added under agitation. The reaction mixture        was agitated at 40° C. for two hours. Then 0.5 g of sodium salt        of dodecylbenzenesulphonic acid (CAS [25155-30-0], Sigma-Aldrich        Norway AS) was added. A clear dispersion with a very good        shelf-life was obtained.

Experiment 35

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   a) 14 g of the reaction product from Experiment 24 was placed in        a borosilicate glass flask (Schott AG, Germany). Then 63 g of        Araldite DY-E (glycidylether of C₁₂-C₁₄-alcohol, Huntsman AG,        Switzerland) was added during agitation and the and the mixture        was agitated in a water bath at 80° C. for 4 hours. The reaction        is strongly exothermic and a clear gel which is viscous at        20° C. and non-viscous at 90° C. is obtained.    -   b) 77 g of the product from a) is reacted in the same        borosilicate flask with 16 g dodecylbenzene sulphonic acid        (Sigma-Aldrich Norway AS). The reaction mixture is agitated in a        water bath at 40 C for one hour. A clear gel which is viscous at        20 C and non-viscous at 90 C is obtained.

Experiment 36

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   560 g of the reaction product from Experiment 24 was heated in a        5 liter reactor to 70° C. Then 1268 g (5.7 moles) of Araldite        DY-E (glycidylether of C₁₂-C₁₄-alcohol, Huntsman AG,        Switzerland) was added and the reaction mixture was heated to        100° C. The reaction is strongly exothermic and by means of the        controllable heat mantle was ensured that the temperature in the        reaction mixture did not exceed 160° C. The procedure was        terminated with vacuum distillation at 20 mbar or less and a        temperature in the reaction mixture of 160° C. A clear product        was obtained which was a viscous gel at 20° C. and a non-viscous        liquid at 90° C.

Experiment 37

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   140 g of the reaction product from Experiment 24 was heated        under agitation in a borosilicate glass flask (Schott AG,        Germany) in a water bath at 70° C. Then 137 g of ε-caprolakctone        (CAS [502-44-3], Sigma-Aldrich Norway AS) was added and the        reaction mixture was heated to 90° C. Two hours later 192 g of        Araldite DY-P (p-tert-butylphenylglycidylether, Huntsman AG,        Switzerland) was added and the reaction mixture was held at        60° C. for 2 hours under agitation. Thereafter the reaction        mixture was agitated at 40° C. for 20 hours. A clear gel which        was a viscous gel at 20° C. and a non-viscous liquid at 120° C.        was obtained.

Experiment 38

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   28 g of the reaction product from Experiment 24 was placed in a        borosilicate glass flask (Schott AG, Germany). Then 39 g        Araldite DY-K (cresylglycidylether, Huntsman AG, Switzerland)        was added under agitation and the reaction mixture was agitated        at ambient temperature. The reaction is strongly exothermic and        a clear gel which was highly viscous at 20° C. and a non-viscous        liquid at 90° C. was obtained.

Experiment 39

Development of the organic branches in a polybranched, organic/inorganichybrid polymer as prepared in Experiment 24.

-   -   a) 28 g of the reaction product from Experiment 24 was placed in        a borosilicate glass flask (Schott AG, Germany). Then 127 g        Araldite DY-E (glycidylether of C₁₂-C₁₄-alcohol, Huntsman AG,        Switzerland) was added under agitation and the reaction mixture        was agitated in a water bath at 80° C. for 4 hours. The reaction        is highly exothermic and a clear gel which was viscous at 20° C.        and non-viscous liquid at 90° C. was obtained.    -   b) 28 g of the reaction product from Experiment 24 was placed in        a borosilicate glass flask (Schott AG, Germany). Then a mixture        of 115 g Araldite DY-E (glycidylether of C₁₂-C₁₄-alcohol,        Huntsman AG, Switzerland) and 12 g of Araldite DY-C        (bisglycidylether of cyklohexane dimethanol, Huntsman AG,        Switzerland) was added under agitation. The reaction mixture was        placed in a water bath at 80° C. The reaction is strongly        exothermic and the reaction mixture is cured to a solid gel that        contrary to the product under a) does not become liquefied when        heated. When heated to above 250° C. the cured reaction product        was clearly degraded.

It is thus clear that the reaction product from b) is not a particulate,polybranched organic/inorganic hybrid polymer according to theinvention.

Experiment 40

Molecular weight analysis with GPC (gel permeation chromatography orsize exclusion chromatography (SEC))

En row of three SEC columns based on 5 μm particles and pore sizes from10000 Å to 100 Å was used in addition to a standard pump and arefractive index detector (RID). Cyclohexane or tetrahydrofuran was usedas mobile phase and solvent respectively. The molecular weight analysisand thereby the Mp values were based on polystyrene standards. Theresults for a number of organic/inorganic hybrid polymers according tothe invention are shown in the table below.

Results based on polystyrene as standards and cyclohexane as mobilephase:

Name: Top 1 Top 2 Top 3 Top 4 Top 1 Top 2 Top 3 Top 4 Mp: Mp: Mp: Mp:Area % Areal % Area % Area % Exp. 26 >1000000* ~6000 ~1000 — 7% 44% 49%— Exp. 28  ~6000 ~3000 ~1000 — 48%  28% 24% — Exp 27 >1000000* ~8000~3000 ~1000 4% 24% 43% 29% *Outside (beyond) the calibration curve.

Results based on polystyrene as standards and tetrahydrofuran as mobilephase:

Navn: Top1 Top2 Top3 Top4 Top5 Top6 Top1 Top2 Top3 Top4 Top5 Top6 Mp:Mp: Mp: Mp: Mp: Mp: Area % Area % Area % Area % Area % Area % Exp.33 >1000000* 31000 — — — — 57% 43% — — — — Exp. 29  ~8000 ~1000 ~900~700 ~600 ~400 40% 29% 6% 9% 9% 7% *Outside (beyond) the calibrationcurve

Experiment 41

An injection moulded sheet of PP-homo polymer (HE125MO, Borealis AS,Norway) was treated with O₂-plasma for 30 seconds (effect 500 W and flux200 standard cm³/min.).

Application of Lacquer:

The lacquer manufacture in Exp. 34 was applied to the plasma treated PPsheet by “bar coating” (rod No. 26). Immediately after coating the sheetwas placed in a convection oven at 120 C for 10 minutes. The sheet wasthereafter removed and cooled in air.

Testing:

The adhesion was determined by use of a standard tape test. A scratchpattern was made by the use of crosshatch cutter (test tool) fromErichsen. The tape was applied to the pattern with an even pressure. Thetape was removed from the sheet and the surface against adhesive wasobserved in an optical microscope. The surface had small or no remainsof the coating.

Experiment 42

Polybranched organic/inorganic hybrid polymer as manufactured inExperiment 38 was heated and applied to a first polyethylene sheet witha thickness of about 100 μm (LLDPE FG5190, Borealis AS, Norway).Immediately thereafter another polyethylene sheet of the same type waspressed onto the top of an organic/inorganic hybrid polymer by means ofa mechanical press at 60° C. The product is a laminateLLPDE—organic/inorganic hybrid polymer—LLDPE. The layer thickness oforganic/inorganic hybrid polymer was during the pressing of the laminatewith a suitable metal frame adjusted to about 500 μm. The laminatelayers exhibited good adhesion to one another.

Experiment 43

The components in the table below were dry blended and a film was blownon a standard labor film blowing machine (nozzle diameter about 25 cm).

PP Foil Melt. Melt Foil Carrier LLDPE HE 125 Nor-X Standard hybrid-thickn. dart press., temp. number bag LD FG5190 MO (eks. 20) whitepolymer μm drop bar ° C. 50303-01 93.5% — — 2.5% 4.0% — — — 356 18850303-02 76.0% 17.5% — 2.5% 4.0% — — — 420 189 50303-03 76.0% 15.0% —5.0% 4.0% — 26-34 226 412 188 50303-04 — 93.5% — 2.5% 4.0% — — — 639 18450303-05 — 91.0% — 5.0% 4.0% — 27-47 125 628 180 50303-06 — 73.5% 20.0%2.5% 4.0% — 28-36 43 324 205 50303-07 — 53.5% 40.0% 2.5% 4.0% — — — 239210 50303-08 — 33.5% 60.0% 2.5% 4.0% — — — 205 214 50303-09 — 13.5%80.0% 2.5% 4.0% — — — 173 217 50303-10 — — 93.5% 2.5% 4.0% — — — 155 21850303-11 — 76.0% 12.5% 2.5% 4.0% 5% VI — — 396 183 50303-12 — 76.0% 7.5%2.5% 4.0% 10% VI 36-55 82 396 193 50303-13 — 76.0% — 2.5% 4.0% 17.5% V35-50 78 379 193 50303-14 — 76.0% 12.5% 2.5% 4.0% 5% I — — 400 19150303-15 — 76.0% 12.5% 2.5% 4.0% 5% II 31-45 70 401 190 50303-16 — 80.0%12.5% 2.5% — 5% III — — 407 189 50303-17 — 80.0% — 2.5% — 17.5% IV 26-3562 403 189 50303-18 — 80.0% 12.5% 2.5% — 5% V — — 399 189 50303-19 —70.0% 17.5% 2.5% — 10% VII 32-49 112 363 189 50303-20 — 80.0% 12.5% 2.5%— 5% VI — 60 400 189Composition:

Carrier bag LD: Polyethylene composition suited for film blowing ofcarrier bags (Norfolier AS, Norway)

FG5190: LLDPE (Borealis AS, Norway)

HE125MO: PP homo polymer (Borealis AS, Norway)

Standard white: Colour masterbatch, ca. 60% titanium dioxide (rutile)and 40% LDPE (Norfolier AS, Norway)

Nor-X: Masterbatch base don 20% of the product from Exp. 20 and 80%LLDPE (Exact Plastomer, ExxonMobil)

Hybrid polymer: Masterbatch base don polybranched organic/inorganichybrid polymer as manufactured according to the Experiments above and PP(HE125MO) and LLDPE (Exact Plastomer, ExxonMobil).

Masterbatch composition is more closely described by the table below (%v/v):

I 20% Exp. 36 i polypropylene II 20% Exp. 36 + 0.5% fat soluble metalcompound Exp. 20 in polypropylene III 20% Exp. 37 in polypropylene IV2.5% Exp. 29 + 12.5% titanium dioxide (rutile) + 0.5% fat-soluble metalcomp. Exp. 20 in polypropylene V 20% Exp. 28 + 0.5% fat-soluble metalcomp. Exp. 20 in polypropylene VI 20% Exp. 30 + 0.5% fat-soluble metalcomp. Exp. 20 in polypropylene VII 10% Exp. 26 + 0.5% fat-soluble metalcomp. Exp. 20 in LLDPE

Dart drop was measured 2 weeks after the foil blowing (ISO 7765-1).

Pressure is specified as measured in the foil extruder.

Temperature specified as measured in the nozzle of the foil extruder.

It is clear that film can be blown on a standard foil extruder of dryblended components of polymer compositions according to the invention.We did not succeed in blowing film under the same conditions from blendsof LLDPE (FG5190) and PP homo polymers (HE125MO), i.e. without afat-soluble metal compound (Exp. 20) according to the invention and/orpolybranched organic/inorganic hybrid polymer as manufactured accordingto the invention.

It is furthermore clear that the dart drop values for the film sampleswith polybranched organic/inorganic hybrid polymer (50303-11-50303-20)are noticeably higher than that of the film sample with correspondingcomposition of LLDPE and PP (50303-6).

Experiment 44

From the hybrid polymer masterbatches I, II and III in Experiment 43injection moulded samples for tensile testing as described in Experiment22. Mechanical testing was conducted as described in Experiment 22. Theresults are shown in the table below:

Hybrid polymer Yield stress Break elongation masterbatch (exp. 43) [MPa][%] I 26.4 ± 0.3 17 ± 3 II 28.8 ± 0.2 160 ± 33 III 28.9 ± 0.7 165 ± 63HE125MO 35.3 ± 0.2  96 ± 62

Experiment 45

Organic/inorganic hybrid polymer as manufactured in the Experiments 25and 33 were used as stabilizers in PP homo polymer (HG430MO, BorealisAS) and compared with a commercial stabilizer (Chimasorb 944, CibaSpecialty Chemicals, Switzerland). Injection moulded samples for tensiletesting were prepared as described in Experiment 22. The compositions ofthe samples are shown below.

Sample PP Exp. 25 Exp. 33 Chimasorb 944 I 99.7% 0.3% — — II 99.1% 0.3%0.6% — III 99.7% — — 0.3%

The samples were exposed to accelerated ageing according to ISO 4892-3.The test instrument was an Atlas UVCON weather-o-meter (Atlas Inc., USA)equipped with UVA-340 fluorescence lamps. The test cycle of “phase A”comprised 4 hours of UV radiation at dry heating to 60° C., 30 minutesof water spraying at 10-12° C. and 3 hours and 30 minutes ofcondensation at 40° C. The test cycle in “phase B” comprised 4 hours ofUV radiation at dry heating to 85° C., 30 minutes of water spraying at10-12° C. and 3 hours and 30 minutes of condensation at 40° C. (thetemperatures as measured by “black panel” thermometer according to ISO4892-3).

Mechanical testing after different ageing periods were conducted asdescribed in Experiment 22. The results are shown in the table below.

Yield str. Yield str. Yield str. Yield str. 3 15 h A + 315 h A + Sample0 h 315 h A 135 h B 301 h B I 35.0 ± 0.3 37.8 ± 0.2 37.5 ± 0.5 37.5 ±1.4 II 35.2 ± 0.3 37.9 ± 0.3 38.7 ± 0.4 38.6 ± 0.6 III 36.2 ± 0.3 37.7 ±0.3 38.3 ± 0.3 38.4 ± 0.2 E-module E-module E-module E-module 315 h A +315 h A + Sample 0 h 315 h A 135 h B 301 h B I 1494 ± 64 1537 ± 31 1658± 110 1660 ± 88 II 1487 ± 35 1561 ± 93 1763 ± 42 1800 ± 40 III 1553 ± 331554 ± 43 1763 ± 72 1667 ± 77 Yield str.: Yield stress [MPa] E-module:Elasticity module [MPa] h: hours of accelerated ageing A: conditions asin “phase A” B: conditions as in “phase B”

Experiment 46

In the same manner as described in Experiment 22 polymer compositionsbased on LLDPE (FG5 190), glass fibre filled polyethylene thereftalate(Rynite PET, DuPont), polystyrene (Empera) andpoly(ethylene-co-vinylacetate) (Escorene Ultra) were prepared. Inaddition Nor-X masterbatch from Experiment 43 was used for half thesample series and LLDPE (Exact 0203 Plastomer, Exxon Mobil) ascompatibility masterbatch in the other half of the sample series.

The relative amounts (% v/v) of components in the polymer compositionsare as follows:

Quality: Rynite PET LLDPE (FG5190) LLDPE Exact 1-a  2% 93% 5% 2-a 10%85% 5% Quality: Empera PS LLDPE (FG5190) LLDPE Exact 3-a  2% 93% 5% 4-a10% 85% 5% Quality: Escorene Ultra EVA LLDPE (FG5190) LLDPE Exact 5-a 2% 93% 5% 6-a 10% 85% 5% Quality: Rynite PET LLDPE (FG5190) Nor-Xmasterbatch 1-b  2% 93% 5% 2-b 10% 85% 5% Quality: Empera PS LLDPE(FG5190) Nor-X masterbatch 3-b  2% 93% 5% 4-b 10% 85% 5% Quality:Escorene Ultra EVA LLDPE (FG5190) Nor-X masterbatch 5-b  2% 93% 5% 6-b10% 85% 5%

The results from the tensile stress test are shown in the table below.

E Module Yield stress Break elongation Material: [N/mm²] [N/mm²] [%] 1-a194 11.1 273 1-b 192 8.7 435 2-a 219 11.2 309 2-b 266 9.5 522 3-a 20111.0 296 3-b 226 11.0 314 4-a 192 10.5 402 4-b 302 11.9 329 5-a 168 11.0296 5-b 207 10.5 285 6-a 187 12.0 250 6-b 188 10.5 275

1. Polymer composition comprising: a) 10-99.99% by weight of at leastone polyolefin, b) up to 50% by weight of a thermoplastic that is not apolyolefin, c) 0.005-1% by weight of per se known polymer additives, d)a fat-soluble iron compound prepared by allowing an iron salt to reactwith an acidic, organic compound in a process in which a suitableoxidation means ensures that all iron in the final product is present inits highest stable oxidation state at standard conditions; and (e) atleast one polybranched organic/inorganic hybrid polymer comprising aninorganic core carrying organic branches that constitute a particlestructure characterized in that the particulate polybranchedorganic/inorganic hybrid polymer is prepared by a sol-gel process, saidsol-gel process comprising at least the following steps in chronologicalsequence; A) the core is made by controlled hydrolysis and condensationof a silane of the structure:X—B—Si(—Y)₃ where X═NR1R2, wherein R1, and R2 are chosen among hydrogen,saturated or unsaturated C1-C18 alkyl, substituted or non-substitutedaryl, in which the carbon chains of said compounds optionally includeone or more of the elements oxygen, nitrogen, sulphur, phosphorous,silicon, and boron and/or optionally containing one or more hydrolysablesilane units, or where R1, and R2 are chosen from condensation productsor addition products of one or more type of chemical compounds such asacids, alcohols, phenols, amines, aldehydes or epoxides, B is a linkagegroup chosen among saturated and unsaturated C1-C18 alkylene,substituted or unsubstituted arylene in which the carbon chains of saidcompounds optionally include one or more branches and/or one or more ofthe elements oxygen, nitrogen, sulphur, phosphorous, silicon, and boron,Y is chosen among hydrolysable residues such as alkoxy, carboxyl,halogen, B) the organic branches are developed by i) when at least oneof R1, and R2 is H, adding at least one reactant that causes N—Hhydrogen atoms of the X—B group of the core to be substituted throughreactions typical for primary and secondary amines, and/or ii) adding anacid that causes an addition to the N atoms of the X—B group of the coreso that the N atoms are wholly or partially converted to quaternarynitronium ions.
 2. Polymer composition as claimed in claim 1,characterized in that component d) and component e) together constitutefrom 0.01 to 90% by weight of the polymer composition.
 3. Polymercomposition as claimed in claim 1, comprising a) 10-99.99% by weight ofat least one polyolefin; b) up to 50% by weight of a thermoplastic thatis not a polyolefin; c) 0.005-1% by weight of per se known polymeradditives; d) a fat-soluble iron compound prepared by allowing an ironsalt to react with an acidic, organic compound in a process in which asuitable oxidation means ensures that all iron in the final product ispresent in its highest stable oxidation state at standard conditions;and (e) at least one polybranched organic/inorganic hybrid polymercomprising an inorganic core carrying organic branches that constitute aparticle structure; characterized in that the particulate, polybranchedorganic/inorganic hybrid polymer is manufactured by a sol-gel processbased on at least partially hydrolysed organic amino-functional silanesprepared by controlled hydrolysis and condensation of a silane of thestructure:X—B—Si(—Y)₃ where X═NR₁R₂, wherein R₁, and R₂ are chosen among hydrogen,saturated or unsaturated C₁-C₁₈ alkyl, substituted or non-substitutedaryl, in which the carbon chains of said compounds optionally includesone or more of the elements oxygen, nitrogen, sulphur, phosphorous,silicon, and boron and/or optionally containing one or more hydrolysablesilane units, or where R₁, and R₂ are chosen from condensation productsor addition products of one or more type of chemical compounds such asacids, alcohols, phenols, amines, aldehydes or epoxides, B is a linkagegroup chosen among saturated and unsaturated C₁-C₁₈ alkylene,substituted or unsubstituted arylene in which the carbon chains of saidcompounds optionally include one or more branches and/or one or more ofthe elements of oxygen, nitrogen, sulphur, phosphorous, silicon, andboron, Y is chosen among hydrolysable residues such as alkoxy, carboxyl,halogen, while N—H hydrogen atoms of the hybrid polymer subsequent tohydrolysis and condensation may be replaced by organic residues,characterized in that the organic branches are prepared by: i) when atleast one of R₁, and R₂ is H, adding at least one reactant that causesN—H hydrogen atoms of the X—B group of the core to be substitutedthrough reactions typical for primary and secondary amines, and/or ii)adding an acid that causes an addition to the N atoms of the X—B groupof the core so that the N atoms are wholly or partially converted toquaternary nitronium ions.
 4. Polymer composition as claimed in claim 1,characterized in that substitution of N—H hydrogen atoms in the branchesorganic/inorganic hybrid polymer in step Bi) is conducted by means of anaddition reaction.
 5. Polymer composition as claimed in claim 1,characterized in that substitution of N—H hydrogen atoms in the branchesorganic/inorganic hybrid polymer in step Bii) is conducted by means of asubstitution reaction.
 6. Polymer composition as claimed in claim 4,characterized in that the addition reaction comprises substitution ofN—H hydrogen atoms by an A=B double bond where A and B are chosen amongthe elements C, O, N, S and P.
 7. Polymer composition as claimed inclaim 4, characterized in that the addition reaction comprises ringopening of an epoxy group.
 8. Polymer composition as claimed in claim 7,characterized in that the ring opening of an epoxy group is followed bythe reaction with a ketone or an aldehyde.
 9. Polymer composition asclaimed in claim 4, characterized in that the addition reactioncomprises substitution of N—H hydrogen atoms by an isocyanate. 10.Polymer composition as claimed in claim 4, characterized in that theaddition reaction comprises ring opening by a cyclic acid anhydride orring opening by a cyclic acid derivative.
 11. Polymer composition asclaimed in claim 10, characterized in that the cyclic acid derivative isa derivative of carbonic acid.
 12. Polymer composition as claimed inclaim 5, characterized in that the substitution reaction comprises areaction with at least one derivative of a linear or cyclic monofunctional carboxylic acid.
 13. Polymer composition as claimed in claim5, characterized in that the substitution reaction comprises a reactionwith at least one derivative of a linear or cyclic mono functionalcarboxylic acid.
 14. Polymer composition as claimed in claim 1,characterized in that the acid being added in step Bii) is a Lewis acidor a Broensted acid.
 15. Polymer composition as claimed in claim 1,characterized in that the substitution of N—H hydrogen atoms in step i)can be conducted in an aqueous medium and/or that the substitution instep ii) is conducted in an aqueous medium.
 16. Polymer composition asclaimed in claim 1, characterized in that the fat-soluble metal compoundis the reaction product of a metal salt and a C₈-C₂₄ fatty acid or aC₈-C₂₄ fatty acid derivative in a process in which a suitable oxidationagent ensures that the metal is present in its highest stable oxidationstate at standard conditions.
 17. Polymer composition comprising; a)10-99.99% by weight of at least one polyolefin; b) up to 50% by weightof a thermoplastic that is not a polyolefin; c) 0.005-1% by weight ofper se known polymer additives; d) a fat-soluble iron compound preparedby allowing an iron salt to react with an acidic, organic compound in aprocess in which a suitable oxidation means ensures that all iron in thefinal product is present in its highest stable oxidation state atstandard conditions; and (e) at least one polybranched organic/inorganichybrid polymer comprising an inorganic core carrying organic branchesthat constitute a particle structure; characterized in that the C₈-C₂₄fatty acid or a C₈-C₂₄ fatty acid derivative is completely or partiallyhalogenated.
 18. Polymer composition as claimed in claim 16,characterized in the C₈-C₂₄ fatty acid or a C₈-C₂₄ fatty acid derivativeis completely or partially unsaturated.
 19. Polymer composition asclaimed in claim 16, characterized in that the oxidation agent ishydrogen peroxide or an organic peroxide.
 20. Polymer compositioncomprising: a) 10-99.99% by weight of at least one polyolefin; b) up to50% by weight of a thermoplastic that is not a polyolefin; c) 0.005-1%by weight of per se known polymer additives; d) a fat-soluble ironcompound prepared by allowing an iron salt to react with an acidic,organic compound in a process in which a suitable oxidation meansensures that all iron in the final product is present in its higheststable oxidation state at standard conditions; and (e) at least onepolybranched organic/inorganic hybrid polymer comprising an inorganiccore carrying organic branches that constitute a particle structure;characterized in that the developed branches in the organic/inorganichybrid polymer include groups that are derivatives of2,2,6,6-tetramethylpiperidine.
 21. Polymer composition comprising: a)10-99.99% by weight of at least one polyolefin; b) up to 50% by weightof a thermoplastic that is not a polyolefin; c) 0.005-1% by weight ofper se known polymer additives; d) a fat-soluble iron compound preparedby allowing an iron salt to react with an acidic, organic compound in aprocess in which a suitable oxidation means ensures that all iron in thefinal product is present in its highest stable oxidation state atstandard conditions; and (e) at least one polybranched organic/inorganichybrid polymer comprising an inorganic core carrying organic branchesthat constitute a particle structure; characterized in the developedbranches in the organic/inorganic hybrid polymer include groups that arederivates of phenol.
 22. Polymer compositions as claimed in claim 1,characterized in that the polymer composition has a substantiallyhomogenous structure (compound).
 23. Polymer compositions as claimed inclaim 1, characterized in that the polymer composition has at least apartially heterogeneous structure.
 24. Polymer composition as claimed inclaim 23, characterized in that the heterogeneous structure comprises alaminate.
 25. Polymer composition as claimed in claim 23, characterizedin that the heterogeneous structure comprises at least two layers thatseparately can be homogenous or heterogeneous.
 26. A molecular barrierlayer for use with gases and liquids comprising the polymer compositionof claim 1, wherein the barrier layer is effective for molecules such aswater, CO₂, oxygen and hydrocarbons.
 27. A flame retardant composition,the composition comprising the polymer composition of claim
 1. 28. Abarrier layer, the barrier layer comprising a polymer compositionpositioned between a first layer comprising a polybranchedorganic/inorganic hybrid polymer and a thermoplastic, wherein thepolymer composition comprises; a) 10-99.99% by weight of at least onepolyolefin; b) up to 50% by weight of a thermoplastic that is not apolyolefin; c) 0.005-1% by weight of per se known polymer additives; d)a fat-soluble iron compound prepared by allowing an iron salt to reactwith an acidic, organic compound in a process in which a suitableoxidation means ensures that all iron in the final product is present inits highest stable oxidation state at standard conditions; and (e) atleast one polybranched organic/inorganic hybrid polymer comprising aninorganic core carrying organic branches that constitute a particlestructure.
 29. The polymer composition of claim 1, further comprising atleast one polybranched organic/inorganic hybrid polymer comprising aninorganic core carrying organic branches that constitute a particlestructure.